1. Technical Field
The field of invention is design, synthesis, use, and devices based on advanced nonlinear optical (NLO) materials.
2. Description of the Related Art
All patents, patent applications, and publications cited within this application are incorporated herein by reference to the same extent as if each individual patent, patent application or publication was specifically and individually incorporated by reference.
The development of chromophores demonstrating nonlinear optical (NLO) properties and the uses thereof, including waveguides incorporating the chromophores and the preparation thereof, and the development of organic polymeric matrices to contain the chromophores, and optical devices incorporating the chromophores/waveguides as well as methods of preparing same, are active areas of research. Disclosures related to these areas have appeared in numerous Patents including the following recently issued U.S. Pat. Nos. 5,272,218; 5,276,745; 5,286,872; 5,288,816; 5,290,485; 5,290,630; 5,290,824; 5,291,574; 5,298,588; 5,310,918; 5,312,565; 5,322,986; 5,326,661; 5,334,333; 5,338,481; 5,352,566; 5,354,511; 5,359,072; 5,360,582; 5,371,173; 5,371,817; 5,374,734; 5,381,507; 5,383,050; 5,384,378; 5,384,883; 5,387,629; 5,395,556; 5,397,508; 5,397,642; 5,399,664; 5,403,936; 5,405,926; 5,406,406; 5,408,009; 5,410,630; 5,414,791; 5,418,871; 5,420,172; 5,443,895; 5,434,699; 5,442,089; 5,443,758; 5,445,854; 5,447,662; 5,460,907; 5,465,310; 5,466,397; 5,467,421; 5,483,005; 5,484,550; 5,484,821; 5,500,156; 5,501,821; 5,507,974; 5,514,799; 5,514,807; 5,517,350; 5,520,968; 5,521,277; 5,526,450; 5,532,320; 5,534,201; 5,534,613; 5,535,048; 5,536,866; 5,547,705; 5,547,763; 5,557,699; 5,561,733; 5,578,251; 5,588,083; 5,594,075; 5,604,038; 5,604,292; 5,605,726; 5,612,387; 5,622,654; 5,633,337; 5,637,717; 5,649,045; 5,663,308; 5,670,090; 5,670,091; 5,670,603; 5,676,884; 5,679,763; 5,688,906; 5,693,744; 5,707,544; 5,714,304; 5,718,845; 5,726,317; 5,729,641; 5,736,592; 5,738,806; 5,741,442; 5,745,613; 5,746,949; 5,759,447; 5,764,820; 5,770,121; 5,76,374; 5,776,375; 5,777,089; 5,783,306; 5,783,649; 5,800,733; 5,804,101; 5,807,974; 5,811,507; 5,830,988; 5,831,259; 5,834,100; 5,834,575; 5,837,783; 5,844,052; 5,847,032; 5,851,424; 5,851,427; 5,856,384; 5,861,976; 5,862,276; 5,872,882; 5,881,083; 5,882,785; 5,883,259; 5,889,131; 5,892,857; 5,901,259; 5,903,330; 5,908,916; 5,930,017; 5,930,412; 5,935,491; 5,937,115; 5,937,341; 5,940,417; 5,943,154; 5,943,464; 5,948,322; 5,948,915; 5,949,943; 5,953,469; 5,959,159; 5,959,756; 5,962,658; 5,963,683; 5,966,233; 5,970,185; 5,970,186; 5,982,958; 5,982,961; 5,985,084; 5,987,202; 5,993,700; 6,001,958; 6,005,058; 6,005,707; 6,013,748; 6,017,470; 6,020,457; 6,022,671; 6,025,453; 6,026,205; 6,033,773; 6,033,774; 6,037,105; 6,041,157; 6,045,888; 6,047,095; 6,048,928; 6,051,722; 6,061,481; 6,061,487; 6,067,186; 6,072,920; 6,081,632; 6,081,634; 6,081,794; 6,086,794; 6,090,322; and 6,091,879. The entire disclosure of these patents is hereby incorporated herein by reference for all purposes.
Despite the attention given to this area, there is a pressing need for improved chromophores that can be used in electro-optic applications and related uses. The present invention is directed to fulfilling this need and providing uses, devices, and communication systems based on non-linear optically active chromophores.
In various aspects, chromophores comprise of novel electron acceptors (A), novel electron donors (D), and/or novel conjugated bridges (p). The chromophores have non-linear optical properties, i.e., are NLO chromophores.
In one aspect, a thiophene-containing chromophore has the structure 
wherein, independently at each occurrence, D is an electron donating group having low electron affinity relative to the electron affinity of A; xcfx801 is absent or a bridge that provides electronic conjugation between D and the thiophene ring; xcfx802 is absent or a bridge that provides electronic conjugation between A and the thiophene ring; A is an electron accepting group having high electron affinity relative to the electron affinity of D; X is O or S; R is alkyl, aryl, heteroalkyl or heteroaryl; and n is 1, 2, 3 or 4.
Specific D groups that may be incorporated into a chromophore include, without limitation, D groups of the following structures, 
wherein, independently at each occurrence, R is alkyl, aryl or heteroalkyl; R1 is hydrogen, alkyl, aryl or heteroalkyl; Y is O, S or Se; m is 2, 3 or 4; p is 0, 1 or 2; and q is 0 or 1. In one embodiment, R contains 1-12 carbons; R1 is hydrogen or contains 1-12 carbons; Y is O or S; m is 2, 3 or 4; p is 0, 1 or 2; and q is 0 or 1. Some preferred D groups that may be present in a chromophore according to the present invention are of the structures: 
In one aspect of the invention, the chromophore contains both xcfx801 and xcfx802 groups, i.e., the xcfx801 and xcfx802 groups are not absent from the chromophore. One or both of xcfx801 and xcfx802 may be, independently at each occurrence, of the structure 
wherein, independently at each occurrence, Z1 is O, S, Se, NR1, C(R1)2 or xe2x80x94C(R1)xe2x95x90C(R1)xe2x80x94; p is 0, 1 or 2; o is 0, 1 or 2; o+p is at least 1; R1 is hydrogen, alkyl, aryl or heteroalkyl;
Z2 is 
and q is 0 or 1.
Some specific structures for xcfx801 and xcfx802 are: 
wherein, independently at each occurrence, R1 is hydrogen, alkyl, aryl or heteroalkyl; Z1 is O, S, Se, NR1, C(R1)2 or xe2x80x94C(R1)xe2x95x90C(R1)xe2x80x94; p is 0, 1 or 2; o is 0, 1 or 2; o+p is at least 1; and q is 0 or 1. In one aspect each of xcfx801 and xcfx802 are xe2x80x94CHxe2x95x90CHxe2x80x94.
Some specific A groups that may be incorporated into chromophores according to the present invention are: 
wherein, independently at each occurrence, R is alkyl, aryl or heteroalkyl; R1 is hydrogen, alkyl, aryl or heteroalkyl; Y is O, S or Se; and q is 0 or 1. Optionally, R contains 1-12 carbons; R1 is hydrogen or contains 1-12 carbons; Y is 0 or S; and q is 0 or 1. A specifically preferred A group is of the formula 
In various aspects of the invention, R is alkyl, and/or aryl, and/or heteroalkyl, and/or heteroaryl, including each and every combination thereof. Optionally, R is hydrophobic, while alternatively R is hydrophilic. Optionally, an R group is saturated, while alternatively an R group is unsaturated. The R group may have, in various aspects of the invention, 1-6 carbons, or 7-12 carbons, or 13-22 carbons.
The value of n may be 1, or 2, or 3, or 4, or each and every combination thereof, e.g., 2 or 3. In one aspect, X is O, while in another aspect X is S.
In one chromophore according to the present invention, xcfx801 and xcfx802 are 
and A is 
wherein R is independently at each occurrence alkyl, aryl or heteroalkyl.
Thus, in one aspect, a thiophene-containing chromophore has of the structure 
wherein, independently at each occurrence, D is selected from the group consisting of 
xcfx801 and xcfx802 are independently 
A is selected from the group consisting of 
X is O or S; R is alkyl, aryl or heteroalkyl; n is 1, 2, 3 or 4; R1 is hydrogen, alkyl, aryl or heteroalkyl; Y is O, S or Se; Z1 is O, S, Se, NR1, C(R1)2 or xe2x80x94C(R1)xe2x95x90C(R1)xe2x80x94;
Z2 is 
q is 0 or 1; p is 0, 1 or 2; o is 0, 1 or 2; o+p is at least 1; and m is 2, 3 or 4.
In another chromophore according to the present invention, D is selected from: 
and xcfx80 is selected from: 
In another aspect, a chromophore has the structure 
wherein, independently at each occurrence, R is alkyl, aryl or heteroalkyl; R1 is alkyl, aryl or heteroalkyl; and X is O or S. For example, R may be xe2x80x94(CH2)wOH, xe2x80x94(CH2)wOR1, xe2x80x94(CH2)wSH, xe2x80x94(CH2)wCO2Et, xe2x80x94(CH2)wCO2H, xe2x80x94(CH2)wNH2, xe2x80x94(CH2)wCN, xe2x80x94(CH2)whalogen, or xe2x80x94COC6H4OCFxe2x95x90CF2 where w is an integer selected from 1-12; and R1 may be hydrogen, R, perfluoroalkyl, SiR3, Si(CH3)2t-Bu, or Si(i-Pr)3.
In another aspect, a chromophore has the structure 
wherein, independently at each occurrence, R is alkyl, aryl or heteroalkyl; R1 is alkyl, aryl or heteroalkyl; and X is O or S. For example, R may be xe2x80x94(CH2)wOH, xe2x80x94(CH2)wOR1, xe2x80x94(CH2)wSH, xe2x80x94(CH2)wCO2Et, xe2x80x94(CH2)wCO2H, xe2x80x94(CH2)wNH2, xe2x80x94(CH2)wCN, xe2x80x94(CH2)whalogen, or xe2x80x94COC6H4OCFxe2x95x90CF2 where w is an integer selected from 1-12; and R1 may be hydrogen, R, perfluoroalkyl, SiR3, Si(CH3)2t-Bu, or Si(i-Pr)3.
In another aspect, a chromophore has a structure 
wherein, independently at each occurrence, D is an electron donating group having low electron affinity relative to the electron affinity of 
xcfx80 is absent or a bridge that provides electronic conjugation between D and the double bond adjacent to xcfx80; and R is alkyl, aryl, heteroalkyl or heteroaryl.
In another aspect, a chromophore has the structure 
wherein R is alkyl, aryl, or heteroalkyl and R1 is hydrogen, alkyl, aryl or heteroalkyl.
In another aspect, a chromophore has the structure 
wherein R is alkyl, aryl, or heteroalkyl and R1 is hydrogen, alkyl, aryl or heteroalkyl.
In another aspect, a chromophore is made by any of the processes illustrated in any of the FIGS. 4A, 4B, 5A, 6A, 7C, 8A, 9A, 10A, 11A, 12A, 13A, 14A, 15A, 16A, 17, 19, 20, 21, 22, 23, 24, and 25.
In another aspect according to the present invention, chromophores or components thereof are provided as shown in any of the FIGS. 1A, 1B, 2A, 2B, 3A, 3B, 4A, 4B, 4C, 5A, 5B, 6A, 6B, 7A, 7B, 7C, 8A, 8B, 9A, 9B, 10A, 10B, 11A, 11B, 12A, 12B, 13A, 13B, 14A, 14B, 15A, 15B, 16A, 16B, 17, 19, 20, 21, 22, 23, 24, and 25.
In another aspect, a composition of matter comprises
Exe2x88x92Ln 
wherein E is a chromophore according to the present invention as set forth herein; L comprises a chemically reactive group that is crosslinkable; and n=1-24. For example, L may represent a thermally crosslinkable trifluorovinylether group. In a composition of matter including Exe2x80x94Ln, in one aspect, at least one of D, xcfx80, or A of the chromophore is covalently bound to a polymer. Optionally, D, a, or A is further substituted with halogen, alkyl, aryl, or heteroalkyl. The chromophore may be non-covalently incorporated into a crosslinkable polymer matrix, or the chromophore may be covalently incorporated into a crosslinked polymer matrix.
According to the present invention a process can comprise sequentially 1) incorporating a chromophore according to the present invention as described herein, into a polymer matrix; 2) maintaining the polymer matrix at a selected temperature to allow effective chromophore mobility; and 3) applying an electric field sufficient to induce an effective amount of dipole alignment of the chromophore in the polymer matrix. A further optional step includes heating the composition to a selected temperature sufficient to affect crosslinking. Embodiments of the present invention also provide compositions of matter prepared by these processes.
The chromophores according to the present invention may be incorporated into many useful devices, e.g., electro-optic devices, waveguides, optical switches, optical modulators, optical couplers, optical router, and generally into communications systems. These devices, or other devices containing chromophores according to the present invention may be used in a method of data transmission wherein light is transmitted through a composition of matter comprising a chromophore according to the present invention. Thus, the present invention provides, in one aspect, a method of telecommunication comprising transmitting light through a composition of matter comprising a chromophore according to the present invention. Such transmission may be accomplished, according to the inventive methods, by directing light through or via a composition of matter comprising a chromophore according to the present invention. Thus, embodiments of the present invention provide, in one aspect, a method of routing light through an optical system comprising transmitting light through or via a composition of matter comprising a chromophore according to the present invention.
In another aspect, an interferometric optical modulator or switch comprises a modulator or switch incorporating an electrooptic polymer or dendrimer. In one embodiment, the modulator or switch includes 1) an input waveguide; 2) an output waveguide; 3) a first leg having a first end and a second end, the first leg being coupled to the input waveguide at the first end and to the output waveguide at the second end; and 4) a second leg having a first end and a second end, the second leg being coupled to the input waveguide at the first end and to the output waveguide at the second end, wherein at least one of the first and second legs comprises a composition of matter comprising a chromophore according to the present invention. The modulator or switch may further comprise an electrode positioned to produce an electric field across the first or second waveguide. While the exemplified modulator or switch is based on a Mach-Zender type of structure, other modulator or switch structures, such as Y-branch structures, evanescent coupling structures, or controlled loss structures, may be within the scope of the invention.
According to the invention, an optical router comprises a plurality of switches, wherein each switch comprises: 1) an input; 2) an output; 3) a first waveguide extending between the input and the output; and 4) a second waveguide aligned to the first waveguide and positioned for evanescent coupling to the first waveguide; wherein at least one of the first and second waveguides comprises a chromophore according to the present invention. Optionally, the plurality of switches is arranged in an array of rows and columns.
These and other aspects according to the present invention are additionally described below.